Benzimidazole derivatives agricultural and horticultural fungicides containing the same as an active ingredient and intermediate compounds thereof

ABSTRACT

A benzimidazole derivative having the formula, ##STR1## wherein R is cyano or thiocarbamoyl; Q is lower alkyl or a group represented by the formula NQ 1  Q 2 , in which Q 1  and Q 2  are independently lower alkyl, lower alkyl substituted with phenyl, lower alkenyl or lower alkynyl, or they form a lower alkylene ring when taken together at their ends which ring may include a hetero atom; X is hydrogen or halogen; and Z is a group which consists of (a) one oxygen atom or two non-adjacent oxygen atom, (b) --CF 2  --group and (c) any one of a single bond, --CF 2  --, --CFH--, CFCl-- and --CH 2  --groups and forms a five-membered or six membered ring together with two adjacent carbon atoms of the benzene ring; is obtained by reacting a corresponding 2-cyanobenzimidazole compound and a sulfamoyl chloride derivative. The benzimidazole derivative is incorporated into agricultural and horticultural fungicides as an active ingredient.

This is a division of application Ser. No. 07/894,007, filed Jun. 2, 1992, now U.S. Pat. No. 5,310,747.

The present invention relates to a benzimidazole derivative, a method for producing it, agricultural and horticultural fungicides containing it as an active ingredient and intermediates for producing it.

Captan, captafol and dithiocarbamate pesticides are known among those which are now widely used as an active ingredient for agricultural and horticultural fungicides, particularly as controlling agents for diseases such as late blight and downy mildew. These pesticides, however, may not always be said to be satisfactory as an active ingredient for agricultural and horticultural fungicides in terms of efficiency and the like.

In view of such situation, the present inventors have extensively studied to develop a compound having excellent efficacy against plant diseases and also giving little phytotoxicity. As a result they have found that the benzimidazole derivative of the present invention has excellent preventive and curative efficacy against plant diseases, is excellent in the systemic activity and further gives no phytotoxicity which would become a problem to crops. The present inventors thus attained to the present invention.

According to the present invention, there are provided a benzimidazole derivative having the formula (I) (hereinafter referred to as present compound), ##STR2## wherein R is cyano or thiocarbamoyl; Q is lower alkyl or a group represented by the formula, NQ¹ Q², in which Q¹ and Q² are independently lower alkyl, lower alkyl substituted with phenyl, lower alkenyl or lower alkynyl, or they form a lower alkylene ring when taken together at their ends which ring may include a hetero atom; X is hydrogen or halogen; and Z is a group which consists of (a) one oxygen atom or two non-adjacent oxygen atoms, (b) --CF₂ --group and (c) any one of a single bond, --CF₂ --, --CFH--, --CFCl-- and --CH₂ --groups and forms a five-membered or six-membered ring together with the two adjacent carbon atoms of the benzene ring; a method for producing it; agricultural and horticultural fungicides containing it as an active ingredient and intermediates for producing it.

In the formula (I), the lower alkyl group represented by Q¹, Q² or Q includes C₁ -C₄ alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, etc.; the lower alkenyl group represented by Q¹ or Q² includes C₃ -C₅ alkenyl groups such as allyl, homoallyl, metaallyl, etc.; the lower alkynyl group represented by Q¹ or Q² includes C₃ -C₅ alkynyl groups such as propargyl, etc.; the lower (usually C₃ -C₈) alkylene ring, formed when Q¹ and Q² are taken together at their ends, which may include a hetero atom (e.g. oxygen atom, sulfur atom) includes butylene, pentylene, CH₂ CH₂ OCH₂ CH₂, CH₂ CH₂ SCH₂ CH₂, etc.; and the halogen atom represented by X includes fluorine, .chlorine, bromine and iodine.

In the formula (I), Q is preferably dimethylamino. Z is preferably --OCF₂ O--, --CF₂ CF₂ O--, OCF₂ CFHO--, --OCF₂ CFClO--, --OCF₂ CF₂ O--, --OCF₂ CH₂ O--, --CF₂ OCF₂ -- or --CF₂ OCF₂ O--.

A method for producing the present compounds will be illustrated in detail.

Among the present compounds, the benzimidazole derivatives having the formula (I) in which R is cyano can be produced by reacting a 2-cyanobenzimidazole compound having the formula (II), ##STR3## wherein X and Z are as defined above, with a sulfonyl chloride derivative having the formula (III)

    Cl--SO.sub.2 Q                                             (III)

wherein Q is as defined above.

In this reaction, the reaction temperature is usually in the range of from room temperature to the refluxing temperature of the solvent, and the reaction time is usually in the range of from a moment to about 24 hours.

This reaction is usually carried out in the presence of a base. Specific examples of the base used are tertiary amines (e.g. pyridine, triethylamine, N,N-dimethylaniline, tributylamine, N-methylmorpholine), inorganic bases (e.g. sodium hydroxide, potassium hydroxide, potassium carbonate) and the like.

Referring to the amounts of the reagents used for the reaction, the amount of the sulfonyl chloride derivative of the formula (III) is usually 1 to 3 moles per mole of the 2-cyanobenzimidazole compound of the formula (II), and that of the base is usually 1 to 7 moles per mole of the compound (II).

The above reaction is usually carried out in the presence of a solvent. Specific examples of the usable solvents are aliphatic hydrocarbons (e.g. hexane, petroleum ether), aromatic hydrocarbons (e.g. benzene, toluene), halogenated hydrocarbons (e.g. chloroform, dichloroethane), ethers (e.g. diethyl ether, dioxane, tetrahydrofuran), ketones (e.g. acetone, methyl ethyl ketone), esters (e.g. ethyl acetate, diethyl carbonate), nitriles (e.g. acetonitrile, isobutyronitrile), amides (e.g. formamide, N,N-dimethylformamide), sulfur compounds (e.g. dimethyl sulfoxide) and the mixtures thereof.

After completion of the reaction, the reaction solution is subjected to usual after-treatments such as extraction with organic solvents, washing with water, concentration of the organic layer under reduced pressure, etc., and then the resulting product is purified if necessary by operations such as chromatography, recrystallization, etc. Thus, the desired present compound can be obtained.

Among the present compounds, the benzimidazole derivatives having the formula (I) in which R is thiocarbamoyl are obtained by reacting the 2-cyanobenzimidazole derivatives having the formula (I) in which R is cyano with hydrogen sulfide.

In this reaction, the reaction time is usually in the range of from a moment to 24 hours, and the reaction temperature is usually in the range of from 0° to 70° C. This reaction is usually carried out in the presence of a base. Specific examples of the base are organic bases such as pyridine, triethylamine, diethylamine, etc. Although a solvent is not always necessary in this reaction, it may be used if necessary. Specific examples of the usable solvent are ethers such as dioxane, tetrahydrofuran, etc.

Referring to the amounts of the reagents used for the reaction, the amount of each of hydrogen sulfide and the base is usually from 1 mole to a large excess per mole of the 2-cyanobenzimidazole derivative.

Among the 2-cyanobenzimidazole compounds having the formula (II), those having no C₂ symmetry axis exhibit tautomerism as shown in the formula (IV), ##STR4## wherein X and Z are as defined above. Therefore, production of the present compounds using those compounds by the above method gives either one of the compounds of the formulae (V) and (VI), ##STR5## wherein R, Q, X and Z are as defined above, or a mixture of the both. Consequently, in the case where the 2-cyanobenzimidazole compounds having the formula (II) have no C₂ symmetry axis, the present compounds of the formula (I) derived therefrom are understood to refer to either one of the compounds having the formulae (V) and (VI) or the mixture thereof.

In the present compounds, when Z forms a five-membered ring together with two carbon atoms of the benzene ring, Z can be expressed as -A₁ -A₂ -A₃ -. When A₁ -A₂ -A₃ and A₃ -A₂ -A₁ are not synonymous with each other (for example, as in the case where Z is --CF₂ CF₂ O--), the compounds having the formula (I) contain two isomers having the formulae (VII) and (VIII), ##STR6## wherein X, R and Q are as defined above, and each of A₁, A₂ and A₃, which may be the same or different, represents one atom or atomic group satisfying the foregoing definition of Z, and A₁ -A₂ -A₃ and A₃ -A₂ -A₁ are different from each other. Those isomers each and their mixture are understood to also be included in the present compounds.

When Z forms a six-membered ring together with two carbon atoms of the benzene ring, Z can be expressed as -B₁ -B₂ -B₃ -B₄ -. When B₁ -B₂ -B₃ -B₄ and B₄ -B₃ -B₂ -B₁ are not synonymous with each other (for example, as in the case where Z is --OCF₂ CFHO--), the compounds having the formula (I) contain two isomers having the formulae (IX) and (X), ##STR7## wherein X, R and Q are as defined above, and each of B₁, B₂, B₃ and B4, which may be the same or different, represents one atom or atomic group satisfying the foregoing definition of Z, and B₁ -B₂ -B₃ -B₄ and B₄ -B₃ -B₂ -B₁ are different from each other. These isomers each and their mixture are understood to also be included in the present compounds.

The 2-cyanobenzimidazole compounds, a starting material for producing the present compounds, having the formula (II) is obtained by reacting a 2-(trichloromethyl)benzimidazole compound having the formula (XI), ##STR8## wherein X and Z are as defined above, with ammonia.

In this reaction, the reaction temperature is usually in the range of from -30° C. to the refluxing temperature of the solvent, and the reaction time is usually in the range of from a moment to about 24 hours.

Referring to the amount of the reagent used for the reaction, the amount of ammonia is usually from 6 moles to a large excess per mole of the 2-(trichloromethyl)benzimidazole compound having the formula (XI).

The above reaction is usually carried out in the presence of a solvent. Specific examples of the usable solvents are aliphatic hydrocarbons. (e.g. hexane, petroleum ether), aromatic hydrocarbons (e.g. benzene, toluene), halogenated hydrocarbons (e.g. chloroform, dichloroethane), ethers (e.g. diethyl ether, dioxane, tetrahydrofuran), ketones (e.g. acetone, methyl ethyl ketone), esters (e.g. ethyl acetate, diethyl carbonate), nitriles (e.g. acetonitrile, isobutyronitrile), amides (e.g. formamide, N,N-dimethylformamide), sulfur compounds (e.g. dimethyl sulfoxide), alcohols (e.g. methanol, ethanol, 2-propanol), water and the mixtures thereof.

After completion of the reaction, the reaction solution is neutralized with an inorganic acid (e.g. hydrochloric acid) and then subjected to after-treatments such as extraction with organic solvents, washing with water, concentration of the organic layer, etc. Thus, the desired compound can be obtained.

The 2-(trichloromethyl)benzimidazole compound having the formula (XI) can be obtained by reacting an o-phenylenediamine compound having the formula (XII), ##STR9## wherein X and Z are as defined above, with a trichloroacetoimidate compound having the formula (XIII), ##STR10## wherein R¹ is lower alkyl.

In this reaction, the reaction temperature is usually in the range of from -30° C. to the refluxing temperature of the solvent, and the reaction time is usually in the range of from a moment to about 24 hours.

Referring to the amount of the reagent used for the reaction, the amount of the trichloroacetoimidate compound having the formula (XIII) is usually 1 to 2 moles per mole of the o-phenylenediamine compound having the formula (XII).

The above reaction is usually carried out in the presence of a solvent. Specific examples of the usable solvent are aliphatic hydrocarbons (e.g. hexane, petroleum ether), aromatic hydrocarbons (e.g. benzene, toluene), halogenated hydrocarbons (e.g. chloroform, dichloroethane), ethers (e.g. diethyl ether, dioxane, tetrahydrofuran), ketones (e.g. acetone, methyl ethyl ketone), nitriles (e.g. acetonitrile, isobutyronitrile), amides (e.g. formamide, N,N-dimethylformamide), sulfur compounds (e.g. dimethyl sulfoxide), alcohols (e.g. methanol, ethanol, 2-propanol), organic acids (e.g. formic acid, acetic acid, propionic acid), and the mixtures thereof.

After completion of the reaction, the reaction solution is subjected, for example, to after-treatments such as pouring into ice water and separation of the resulting crystals by filtration, or extraction with organic solvents, washing with water, concentration, etc. The resulting product is then purified if necessary by operations such as chromatography, recrystallization, etc. Thus, the desired compound can be obtained.

The 2-(trichloromethyl)benzimidazole compound having the formula (XI) can also be obtained by reacting the o-phenylenediamine compound having the formula (XII) with trichloroacetyl chloride to obtain a 2-aminotrichloroacetoanilide compound and subjecting the 2-aminotrichloroacetoanilide compound to cyclization reaction.

In this cyclization reaction, the reaction temperature is usually in the range of from 40° C. to the refluxing temperature of the solvent, and the reaction time is usually in the range of from a moment to about 24 hours.

The above reaction is usually carried out in the presence of a solvent. Specific examples of the solvents usable for the reaction are aliphatic hydrocarbons (e.g. hexane, petroleum ether), aromatic hydrocarbons (e.g. benzene, toluene), halogenated hydrocarbons (e.g. chloroform, dichloroethane), ethers (e.g. diethyl ether, dioxane, tetrahydrofuran), ketones (e.g. acetone, methyl ethyl ketone), esters (e.g. ethyl acetate, diethyl carbonate), nitriles (e.g. acetonitrile, isobutyronitrile), amides (e.g. formamide, N,N-dimethylformamide), sulfur compounds (e.g. dimethyl sulfoxide), alcohols (e.g. methanol, ethanol, 2-propanol), water and the mixtures thereof.

The reaction of the o-phenylenediamine compound of the formula (XI) with trichloroacetyl chloride can be carried out in the same manner as in the reaction of the 2-cyanobenzimidazole compound of the formula (II) with the sulfonyl chloride compound of the formula (III).

The o-phenylenediamine derivative having the formula (XII) can be Obtained by reducing an o-nitroaniline compound having the formula (XIV), ##STR11## wherein X and Z are as defined above.

The reduction method which can be used includes, for example, a method of carrying out reduction using sodium sulfide or sodium hydrogensulfide in a mixture of water and a lower alcohol such as methanol, ethanol, etc. The reaction temperature is usually in the range of from 50° C. to the refluxing temperature of the solvent, and the reaction time is usually within 12 hours.

Also, this reduction can be carried out by a method using iron powders, zinc powders or tin powders in a mixture of water and either an organic acid (e.g. acetic acid) or an inorganic acid (e.g. hydrochloric acid, sulfuric acid). This reaction is usually carried out at from 30° to 100° C. and within 12 hours.

Further, a method of carrying out hydrogenation in the temperature range of usually from 0° to 60° C. at normal pressure or under pressure using a catalyst (e.g. platinum dioxide, palladium-carbon) in an organic solvent (e.g. ethanol, ethyl acetate) can also be used.

The o-phenylenediamine compound having the formula (XII) can also be obtained by reducing an o-dinitro compound having the formula (XV), ##STR12## wherein X and Z are as defined above.

The reduction method includes, for example, a method described in JP-A-62-198678 and a method of carrying out hydrogenation in the temperature range of usually from 0° to 60° C. at normal pressure or under pressure in an organic solvent (e.g. ethanol, ethyl acetate) using a catalyst such as platinum dioxide, palladium-carbon and the like.

Some of the compounds having the formula (XV) are disclosed in JP-A-62-198678. The rest of the compounds having the formula (XV) can be prepared by the same method as described in JP-A-62-198678 starting from a 1,2-difluoromethylenedioxybenzene derivative, a fluorinated benz-1,4-dioxene derivative or the like.

The o-nitroaniline compound having the formula (XIV) is obtained by hydrolyzing an o-nitroanilide compound having the formula (XVI), ##STR13## wherein X and Z are as defined above, and R² is lower alkyl.

The reaction temperature is usually in the range of from room temperature to 100° C. or the refluxing temperature of the solvent, and the reaction time is usually in the range of from a moment to about 24 hours.

The above reaction is usually carried out in the presence of a base or acid. Specific examples of the base are inorganic bases such as sodium hydroxide, potassium hydroxide, etc. Specific examples of the acid are inorganic acids such as hydrochloric acid, sulfuric acid, etc.

Referring to the amount of the reagent used for the reaction, the amount of the base or acid is from a catalytic amount to a large excess per mole of the o-nitroanilide compound having the formula (XVI).

The reaction is carried out with or without a solvent depending upon the kind of the base or acid used. Specific examples of the usable solvent are aliphatic hydrocarbons (e.g. hexane, petroleum ether), aromatic hydrocarbons (e.g. benzene, toluene), halogenated hydrocarbons (e.g. chloroform, dichloroethane), ethers (e.g. diethyl ether, dioxane, tetrahydrofuran), ketones (e.g. acetone, methyl ethyl ketone), nitriles (e.g. acetonitrile, isobutyronitrile), amides (e.g. formamide, N,N-dimethylformamide), sulfur compounds (e.g. dimethyl sulfoxide), alcohols (e.g. methanol, ethanol, 2-propanol), organic acids (formic acid, acetic acid, propionic acid), water and the mixtures thereof.

The o-nitroaniline compound of the formula (XIV) wherein X is chlorine or bromine can also be obtained by chlorinating or brominating a compound having the formula (XVII), ##STR14## wherein Z is as defined above.

In this reaction, the reaction temperature is usually in the range of from 0° C. to the refluxing temperature of the solvent, and the reaction time is usually in the range of from a moment to about 24 hours.

Referring to the amount of the reagents used for the reaction, the amount of the chlorinating or brominating agent is from 1 mole to a large excess per mole of the compound having the formula (XVII).

Chlorine, N-chlorosuccinimide, sulfuryl chloride, etc. can be used as a chlorinating agent. Bromine, N-bromosuccinimide, etc. can be used as a brominating agent.

Specific examples of the solvent usable for this reaction are halogenated hydrocarbons (e.g. chloroform, carbon tetrachloride, dichloroethane), ethers (e.g. diethyl ether, dioxane, tetrahydrofuran), organic acids (e.g. formic acid, acetic acid, propionic acid), water and the mixtures thereof.

The o-nitroanilide compound having the formula (XVII) can be obtained by nitrating an anilide compound having the formula (XVIII), ##STR15## wherein X, Z and R² are as defined above.

In this reaction, the reaction temperature is usually from -40° C. to 20° C., and the reaction time is usually from a moment to 24 hours.

As the nitrating agent, fuming nitric acid, nitric acid, sodium nitrate and potassium nitrate can be used. As the solvent, acetic acid, acetic anhydride, sulfuric acid, fuming sulfuric acid, water and the mixtures thereof can be used.

Referring to the amount of the reagent used for the reaction, the amount of the nitrating agent is from 1 mole to a large excess per mole of the compound represented by the formula (XVIII).

Among the o-nitroanilide compounds having the formula (XVI), the compounds having the formula (XIX), ##STR16## wherein R² is lower alkyl, can also be obtained by cyclization of a compound having the formula (XX), ##STR17## wherein Y is bromine or chlorine, and R² is lower alkyl, in the presence of metallic copper.

The reaction temperature is usually in the range of from 50° C. to the refluxing temperature of the solvent, and the reaction time is usually in the range of from a moment to 24 hours.

The amount of copper used for the reaction is usually from 2 moles to a large excess per mole of the compound having the formula (XIX).

The above reaction is usually carried out in a solvent. Specific examples of the usable solvent are amides (e.g. formamide, N,N-dimethylformamide), sulfur compounds (e.g. dimethyl sulfoxide) and the mixtures thereof.

After completion of the reaction, the reaction solution is for example filtered and then subjected to after-treatments such as extraction of the filtrate with an organic solvent, washing with water, concentration, etc. The product obtained is purified if necessary by operations such as chromatography, recrystallization, etc. Thus, the desired compound can be obtained.

The anilide compound having the formula (XVIII) can be obtained by acylating an aniline compound having the formula (XXI), ##STR18## wherein X and Z are as defined above.

The reaction temperature is usually in the range of from room temperature to 120° C. or the refluxing temperature of the solvent, and the reaction time is usually in the range of from a moment to about 24 hours.

This reaction is usually carried out in the presence of a base or acid. Specific examples of the base used are tertiary amines (e.g. pyridine, triethylamine, N,N-dimethylaniline, tributylamine, N-methylmorpholine), inorganic bases (e.g. sodium hydroxide, potassium hydroxide, potassium carbonate) and the like. Specific examples of the acid are organic acids (e.g. formic acid, acetic acid, propionic acid) and inorganic acids (e.g. sulfuric acid).

The amount of the base or acid used for the reaction is from a catalytic amount to a large excess per mole of the aniline compound having the formula

Specific examples of the acylating agent used in the above reaction are corresponding acid anhydrides, acid halides, ester compounds, carboxylic acids, etc.

The amount of the acylating agent used for the reaction is from 1 mole to a large excess per mole of the aniline compound having the formula (XXI).

The solvent used is determined depending upon the base or acid used. When the solvent is used, it includes aliphatic hydrocarbons (e.g. hexane, petroleum ether), aromatic hydrocarbons (e.g. benzene, toluene), halogenated hydrocarbons (e.g. chloroform, dichloroethane), ethers (e.g. diethyl ether, dioxane, tetrahydrofuran), ketones (e.g. acetone, methyl ethyl ketone), esters (e.g. ethyl acetate), nitriles (e.g. acetonitrile, isobutyronitrile), amides (e.g. formamide, N,N-dimethylformamide), sulfur compounds (e.g. dimethylsulfoxide), organic acids (e.g. formic acid, acetic acid, propionic acid) and the mixtures thereof.

Among the compounds having the formula (XVIII), compounds having the formula (XXII), ##STR19## wherein R² represents a lower alkyl group, are obtained by cyclization of a compound having the formula (XXIII), ##STR20## wherein Y¹ and Y² are independently hydrogen, bromine or chlorine provided that Y¹ and Y² are not a hydrogen atom at the same time, and R² is lower alkyl, with metallic copper.

This cyclization reaction can be carried out in the same manner as in the cyclization of the compound having the formula (XX).

The aniline compound having the formula (XXI) is disclosed or can be produced by the methods described, for example, in Liebigs Ann. Chem., 730, 16-30 (1969), and JP-A-55-69576, U.S. Pat. No. 4,767,779, Chemical Abstracts, 60, 13352h etc.

Other than the method described above, the o-nitroaniline compound having the formula (XVII) can also be prepared by reacting a compound having the formula (XXIII), ##STR21## wherein Z is as defined above, Y³ is nitro or halogen, with ammonia.

In this reaction, the reaction temperature is usually within the range of from 0° C. to the refluxing temperature of the solvent, and the reaction time is usually within the range of from a moment to about 24 hours.

Referring to the amount of the reagents used for the reaction, the amount of ammonia is from 1 mole to a large excess per mole of the compound having the formula (XXIII).

Specific examples of the solvent usable for this reaction are aliphatic hydrocarbons (e.g. hexane, petroleum ether), aromatic hydrocarbons (e.g. benzene, toluene), ethers (e.g. diethylether, dioxane, tetrahydrofuran), amides (e.g. formamide, N,N-dimethylformamide), sulfur compounds (e.g. dimethyl sulfoxide), alcohols (e.g. methanol, ethanol, 2-propanol), water and the mixtures thereof.

Some of the compounds having the formula (XXIII) are disclosed in Chemical Abstracts, 60, 13353c (1964) or in JP-A-62-198678. The rest of the compounds having the formula (XXIII) can be prepared by the same method as described in JP-A-62-198678 starting from 1,2-difluoromethylenedioxybenzene or the like.

The present compound itself may be used as an active ingredient for agricultural and horticultural fungicides without adding any other ingredients. Usually, however, it is formulated into emulsifiable concentrates, wettable powders, suspension formulations, dusts, granules, dry flowable formulations, etc. by mixing with solid carriers, liquid carriers, gaseous carriers, surface active agents and other auxiliaries for formulation. In this case, the content of the present compound, which is an active ingredient, in the formulations is usually from 0 01 to 99% , preferably from 0.1 to 80%.

Specific examples of the solid carriers are fine powders or granules of clays (e.g. kaolin clay, diatomaceous earth, synthetic hydrated silicon dioxide, Fubasami clay, bentonire, terra alba), talcs, other inorganic minerals (e.g. sericite, calcite powder, quartz powder, activated carbon, calcium carbonate, hydrated silica), chemical fertilizers (e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, ammonium chloride), corn stalk powder, walnut shell powder, etc. Specific examples of the liquid carriers are water, alcohols (e.g. methanol, ethanol, ethylene glycol, cellosolve), ketones (e.g. acetone, methyl ethyl ketone, isophorone), aromatic hydrocarbons (e.g. benzene, toluene, xylene, ethylbenzene, methylnaphthalene), aliphatic hydrocarbons (e.g. n-hexane, cyclohexane, kerosene, gas oil), esters (e.g. ethyl acetate, butyl acetate), nitriles (e.g. acetonitrile, isobutyronitrile), ethers (e.g. dioxane, diisopropyl ether), acid amides (e.g. dimethylformamide, dimethylacetamide), halogenated hydrocarbons (e.g. dichloroethane, trichloroethylene, carbon tetrachloride), vegetable oils (e.g. soybean oil, cotton seed oil), dimethyl sulfoxide, etc. Specific examples of the gaseous carriers, i.e. a propellant, are freon gas (registered trade name), butane gas, carbon dioxide gas, etc.

Specific examples of the surface active agents are anionic surface active agents such as alkyl sulfates, alkylaryl esters, alkylsulfonates, alkylarylsulfonates, dialkyl sulfosuccinates, the salts of a polyoxyethylene alkylaryl ether phosphoric acid ester, naphthalenesulfonic acid/formalin condensates, etc. and nonionic surface active agents such as polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters, polyhydric alcohol esters, sugar alcohol derivatives, etc.

Specific examples of the fixing agents and dispersing agents are casein, gelatin, polysaccharides [e.g. starch powder, gum arabic, cellulose derivatives {e.g. CMC (carboxymethyl cellulose)}, lignin derivatives {e.g. lignosulfonate}, alginic acid], bentonire, synthetic water-soluble high polymers (e.g. polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acids), etc. Specific examples of the stabilizing agents are PAP (isopropyl acid phosphate), BHT (2,6-di-tert-butyl-4-methylphenol), BHA (a mixture of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol), vegetable oils, mineral oils, surface active agents, fatty acids and their esters, etc.

The application methods for the present compound are foliar application, soil treatment, seed disinfection and the like. However, any application method which is commonly used by the skilled artisan may be used.

When the present compound is used as an active ingredient for agricultural and horticultural fungicides, the dosage rate of the active ingredient varies with target crops, target diseases, degrees of outbreak of diseases, preparation forms, application methods, application times, weather conditions, etc. Usually, however, the dosage rate is 0.01 to 50 g/are, preferably 0.05 to 10 g/are. When the emulsifiable concentrates, wettable powders, suspension formulations, dry flowable concentrates, etc. are applied diluted with water, the application concentration of the active ingredient is 0.0001 to 0.5%, preferably 0.0005 to 0.2%. The dusts, granules, etc. are applied as they are without being diluted.

As plant diseases which can be controlled with the present compound, for example, the following ones can be given.

Downy mildew of vegetables and Japanese radish (Peronospora brassicae), downy mildew of spinach (Peronospora spinaciae), downy mildew of tobacco (Peronospora tabacina), downy mildew of cucumber (Pseudoperonospora cubensis), downy mildew of grape (Plasmopara viticola), late blight of apple, strawberry and ginseng (Phytophthora cactorum), phytophthora rot of tomato and cucumber (Phytophthora capsici), late blight of pineapple (Phytophthora cinnamomi), late blight of potato, tomato and eggplant (Phytophthora infestans), late blight of tobacco, broad bean and Welsh onion (Phytophthora nicotianae var. nicotianae), damping-off of spinach (Pythium sp.), damping-off of cucumber (Pythium aphanidermatum), browning root rot of wheat (Pythium sp.), damping-off of tobacco (Pythium debaryanum) and Pythium rot of soybean (Pythium aphanidermatum, P. debaryanum, P. irregulare, P. myriotylum, P. ultimum).

The present compound can be used as agricultural and horticultural fungicides in plow fields, paddy fields, orchards, tea gardens, pastures, turfs, etc. It can also be used in mixture with other agricultural and horticultural fungicides. Further, it can also be used in mixture with insecticides, acaricides, nematocides, herbicides, plant growth regulators and fertilizers.

The present compounds have excellent preventive and curative effect particularly on various diseases caused by Phycomycetes. One or more of the present compounds can be mixed with at least one fungicidal active ingredient selected from the group consisting of chlorothalonil, fluazinam, dichlofluanide, phosethyl-aluminum, cyclic imide fungicides (e.g. captan, captafol, folpet), dithiocarbamate fungicides (e.g. maneb, mancozeb, thiram, ziram, zineb, propineb), inorganic or organic copper fungicides (e.g. basic cupric sulfate, basic cupric chloride, cupric hydroxide, oxine-copper), cymoxanil, acylalanine fungicides (e.g. metalaxyl, furalaxyl, ofurace, cyprofuram, benalaxyl, oxadixyl) and compounds disclosed in JP-A-1-301681 (e.g. N-[cyano(2'-furyl)methyl]-2,4-dimethylthiazole-5-carboxyamide, N-[cyano(3'-furyl)methyl]-2,4-dimethyl-thiazole-5-carboxyamide, N-[cyano(2'-thienyl)methyl]-2,4-dimethylthiazole-5-carboxyamide, N-[cyano(3'thienyl)methyl]-2,4-dimethylthiazole-5-carboxyamide, N-[cyano(2'-furyl)methyl]-2-methyl-4-ethylthiazole-5-carboxyamide, N-[cyano(3'-furyl)methyl]-2-methyl-4-ethylthiazole-5-carboxyamide, N-[cyano(2'-thienyl)methyl]2-methyl-4-ethylthiazole-5-carboxyamide and N-[cyano(3'-thienyl)methyl]-2-methyl-4-ethylthiazole-5-carboxyamide. The resulting mixture can be used as a fungicide in the same manner for the present compounds as described above. Hereupon, the mixing ratios of the present compound(s) to chlorothalonil, fluazinam, dichlofluanide, phosethyl-aluminum, cyclic imide fungicides, dithiocarbamate fungicides or the inorganic or organic copper fungicides are usually within the range of from 1: 1 to 1: 200 in terms of the weight of the active ingredient. The mixing ratios of the present compound(s) to cymoxanil, the acylalanine fungicides or compounds disclosed in JP-A-1-301681 are usually within the range of from 1:0.1 to 1:20 in terms of the weight of the active ingredient. In this case, these active ingredients can be used by mixing them and then formulating as described above, or by formulating each of them as described above and then mixing. Use of the present compound(s) in mixture with other fungicide(s) as above is expected to synergistically improve the efficacy particularly on various diseases caused by Phycomycetes.

The present invention will be illustrated in more detail with reference to the following production examples, formulation examples and test examples. However, the present invention is not to be interpreted as being limited thereto.

Production Example 1

2.83 Grams of a 2-cyanobenzimidazole compound [compound (i)] of the formula (II) in which X is H and Z is OCF₂ CFHO was dissolved in 50 ml of acetonitrile. 3.8 Grams of potassium carbonate was added thereto. The resulting mixture was heated under reflux for 15 minutes. Thereafter, 2.6 g of dimethylsulfamoyl chloride was added to the refluxed mixture. Refluxing was continued for additional 40 minutes with heating. The reaction solution was poured into ice water and extracted with ethyl acetate. The organic layer was washed with water and dried over anhydrous sodium sulfate. A residue was obtained by removing the solvent from the dried layer by distillation. Column chromatographying the residue on silica gel with toluene as an eluent gave 1.53 g of a benzimidazole derivative [present compound (1)] of the formula (I) in which X is H, Z is OCF₂ CFHO, R is CN and Q is N(CH₃)₂.

Production Example 2

0.95 Gram of the present compound (1) was dissolved in 20 ml of pyridine. The resulting solution was stirred for 1 hour and 45 minutes in a hydrogen sulfide atmosphere. After reaction, the reaction solution was extracted with ethyl acetate. The organic layer was washed with water and dried over anhydrous sodium sulfate. Crystals were obtained by removing the solvent from the dried layer by distillation. Column chromatographying the crystals on silica gel with a chloroform/ethyl acetate mixed solution as an eluent and recrystallizing them from hexane/ethyl acetate gave 0.83 g of a benzimidazole derivative [present compound (4)] of the formula (I) in which X is H, Z is OCF₂ CFHO, R is thiocarbamoyl and Q is N(CH₃)₂.

Production Example 3

1.8 Grams of a 2-cyanobenzimidazole compound [compound (iii)] of the formula (II) in which X is Br and Z is OCF₂ CFHO was dissolved in 70 ml of acetonitrile. 1.5 Grams of potassium carbonate was added thereto. The resulting mixture was heated under reflux for 20 minutes. Thereafter, 1.2 g of dimethylsulfamoyl chloride was added thereto. Refluxing was continued for 1 hour with heating. The reaction solution was poured into ice water and extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous sodium sulfate and concentrated. Column chromatographying the resulting residue on silica gel with chloroform as an eluent and recrystallizing it from hexane/ethyl acetate gave 1.18 g of a benzimidazole derivative [present compound (3)] of the formula (I) in which X is Br, Z is OCF₂ CFHO, R is CN and Q is N(CH₃)₂.

Production Example 4

1.5 Grams of a 2-cyanobenzimidazole compound [compound (ii)] of the formula (II) in which X is F and Z is OCF₂ CFHO was dissolved in 50 ml of acetonitrile. 2.0 Grams of potassium carbonate was added thereto. The resulting mixture was heated under reflux for 25 minutes. Thereafter, 1.5 g of dimethylsulfamoyl chloride was added thereto. Refluxing was continued for 40 minutes with heating. The reaction solution was poured into ice water and extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous sodium sulfate and concentrated. Column chromatographying the resulting residue on silica gel with toluene as an eluent and recrystallizing it from hexane/ethyl acetate gave 0.9 g of a benzimidazole derivative [present compound (2)] of the formula (I) in which X is F, Z is OCF₂ CFHO, R is CN and Q is N(CH₃)₂ (bubble-form compound).

Production Example 5

6.2 Grams of a 2-cyanobenzimidazole compound [compound (iv)] of the formula (II) in which X is H and Z is OCF₂ O was dissolved in 100 ml of acetonitrile. 10 Grams of potassium carbonate was added thereto. The resulting mixture was heated under reflux for 15 minutes. Thereafter, 6.7 g of dimethylsulfamoyl chloride was added thereto. Refluxing was continued for 15 minutes with heating. The reaction solution was poured into ice water and extracted with ethyl acetate. The organic layer was washed with water and dried over anhydrous sodium sulfate. Crystals were obtained by removing the solvent from the dried layer by distillation. Recrystallizing the crystals from hexane/ethyl acetate and then from chloroform/methanol gave 2.4 g of benzimidazole derivative [present compound (15)] of the formula (I) in which X is H, Z is OCF₂ O, R is CN and Q is N(CH₃)₂.

Production Example 6

0.4 Gram of the present compound (15) was dissolved in 10 ml of pyridine and reacted for 2 hours and 30 minutes in a hydrogen sulfide atmosphere. After reaction, the reaction solution was distributed between ethyl acetate and water. The organic layer was washed with water and dried over anhydrous sodium sulfate. Crystals were obtained by removing the solvent by distillation. Recrystallizing the crystals from hexane/ethyl acetate gave 0.24 g of a benzimidazole derivative [present compound (18)] of the formula (I) in which X is H, Z is OCF₂ O, R is thiocarbamoyl and Q is N(CH₃)₂.

Production Example 7

1.5 Grams of a 2-cyanobenzimidazole compound [compound (vi)] of the formula (II) in which X is Br and Z is OCF₂ O was dissolved in 60 ml of acetonitrile. 2.0 Grams of potassium carbonate was added thereto. The resulting mixture was heated under reflux for 15 minutes. Thereafter, 2.0 g of dimethylsulfamoyl chloride was added thereto. Refluxing was continued for 15 minutes with heating. The reaction solution was poured into ice water and extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous sodium sulfate and concentrated. Column chromatographying the resulting residue on silica gel with chloroform as an eluent and recrystallizing it from hexane/ethyl acetate gave 1.3 g of benzimidazole derivative [present compound (17)] of the formula (I) in which X is Br, Z is OCF₂ O, R is CN and Q is N(CH₃)₂.

The benzimidazole derivative obtained above was further recrystallized from toluene. X-ray analysis of the recrystallized benzimidazole demonstrated that it was one of the regio isomers and contained the SO₂ N(CH₃)₂ group attached to one of the nitrogen atoms constituting the benzimidazole ring furthest from the bromine atom.

Production Example 8

2.05 Grams of a 2-cyanobenzimidazole compound of the formula (II). in which X is F and Z is OCF₂ O was dissolved in 50 ml of acetonitrile. 2.0 Grams of potassium carbonate was added thereto. The resulting mixture was heated under reflux for 20 minutes. Thereafter, 1.3 g of dimethylsulfamoyl chloride was added thereto. Refluxing was continued for 45 minutes with heating. The reaction solution was poured into ice water and extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous sodium sulfate and concentrated. Column chromatographying the resulting residue on silica gel with chloroform as an eluent and recrystallizing it from hexane/ethyl acetate gave 1.33 g of benzimidazole derivative [present compound (16)] of the formula (I) in which X is F, Z is OCF₂ O, R is CN and Q is N(CH₃)₂.

Production Example 9

0.6 Gram of a 2-cyanobenzimidazole compound of the formula (II) in which X is H and Z is CF₂ CF₂ O was dissolved in 30 ml of acetonitrile. 0.75 Gram of potassium carbonate was added thereto. The resulting mixture was heated under reflux for 20 minutes. Thereafter, 0.4 g of dimethylsulfamoyl chloride was added thereto. Refluxing was continued for 1 hour with heating. The reaction solution was poured into ice water and extracted with ethyl acetate. The organic layer was washed with water and dried over anhydrous sodium sulfate. A residue was obtained by removing the solvent from the dried layer by distillation. Column chromatographying the residue on silica gel with toluene as an eluent gave 0.23 g of a benzimidazole derivative [present compound (29)] of the formula (I) in which X is H, Z is CF₂ CF₂ O, R is CN and Q is N(CH₃)₂. ¹ H-NMR spectrum showed that the product was a mixture of two regio isomers.

Examples of the present compound which can be produced by the above methods will be shown in Tables 1 to 9.

                                      TABLE 1                                      __________________________________________________________________________     Benzimidazole derivatives having the formula (I):                                                          .sup.1 H-NMR                                                                   (Internal                                          Com-                   Melting                                                                             standard: TMS)                                     pound                  point                                                                               Solvent:                                           No. X Z      R    Q    (°C.)                                                                        δ (ppm)                                      __________________________________________________________________________     (1) H OCH.sub.2 CFHO                                                                        CN   N(CH.sub.3).sub.2                                                                   115-118                                                                             CDCl.sub.3 ; 7.75(1H, s)                                                       7.62(1H, s)                                                                    6.50(1H, dt, J=52, 2Hz)                                                        3.10(6H, s)                                        (2) F OCH.sub.2 CFHO                                                                        CN   N(CH.sub.3).sub.2                                                                        CDCl.sub.3 ;                                                                   7.55(1H, d, J=2Hz)                                                             6.10(1H, dt, J=52, 2Hz)                                                        3.10(6H, s )                                       (3) Br                                                                               OCH.sub.2 CFHO                                                                        CN   N(CH.sub.3).sub.2                                                                        DMSO-d.sub.6 ; 7.80(1H, s)                                                     7.05(1H, dt, J=50, 1Hz)                                                        3.10(6H, s)                                        (4) H OCH.sub.2 CFHO                                                                        CSNH.sub.2                                                                          N(CH.sub.3).sub. 2                                                                  177-179                                                                             CDCl.sub.3 + DMSO-d.sub.6 ;                                                    9.3(2H, br) 7.6(1H, s)                                                         7.45(1H, s)                                                                    6.05(1H, dt, J=54, 3Hz)                                                        3.05(6H, s)                                        __________________________________________________________________________

                                      TABLE 2                                      __________________________________________________________________________     Benzimidazole derivatives having the formula (I):                                                            .sup.1 H-NMR                                                                   (Internal                                                                 Melting                                                                             standard: TMS)                                   Compound                 point                                                                               Solvent:                                         No.   X Z      R    Q    (°C.)                                                                        δ (ppm)                                    __________________________________________________________________________      (5)  F OCF.sub.2 CFHO                                                                        CSNH.sub.2                                                                          N(CH.sub.3).sub.2                                           (6)  Br                                                                               OCF.sub.2 CFHO                                                                        CSNH.sub.2                                                                          N(CH.sub.3).sub.2                                           (7)  H OCF.sub.2 CF.sub.2 O                                                                  CN   N(CH.sub.3).sub.2                                           (8)  F OCF.sub.2 CF.sub.2 O                                                                  CN   N(CH.sub.3).sub.2                                           (9)  Br                                                                               OCF.sub.2 CF.sub.2 O                                                                  CN   N(CH.sub.3).sub.2                                          (10)  F OCF.sub.2 CF.sub.2 O                                                                  CSNH.sub.2                                                                          N(CH.sub.3).sub.2                                          (11)  H OCF.sub.2 CH.sub.2 O                                                                  CN   N(CH.sub.3).sub.2                                          (12)  F OCF.sub.2 CH.sub.2 O                                                                  CN   N(CH.sub.3).sub.2                                          (13)  H OCF.sub.2 CFClO                                                                       CN   N(CH.sub.3).sub.2                                          (14)  F OCF.sub.2 CFClO                                                                       CN   N(CH.sub.3).sub.2                                          __________________________________________________________________________

                                      TABLE 3                                      __________________________________________________________________________     Benzimidazole derivatives having the formula (I):                                                          .sup.1 H-NMR                                                                   (Internal                                          Com-                 Melting                                                                               standard: TMS)                                     pound                point  Solvent:                                           No. X Z    R    Q    (°C.)                                                                          δ (ppm)                                      __________________________________________________________________________     (15)                                                                               H OCF.sub.2 O                                                                         CN   N(CH.sub.3).sub.2                                                                   187-194                                                                               DMSO-d.sub.6 ; 8.05(1H, s)                                              decomposed                                                                            8.00(1H, s) 3.05(6H, s)                            (16)                                                                               F OCF.sub.2 O                                                                         CN   N(CH.sub.3).sub.2                                                                   165-170                                                                               DMSO-d.sub.6 ; 7.90(1H, s)                                              decomposed                                                                            3.10(6H, s)                                        (17)                                                                               Br                                                                               OCF.sub.2 O                                                                         CN   N(CH.sub.3).sub.2                                                                   195-200                                                                               DMSO-d.sub.6 ; 8.00(1H, s)                                              decomposed                                                                            3.05(6H, s)                                        (18)                                                                               H OCF.sub.2 O                                                                         CSNH.sub.2                                                                          N(CH.sub.3).sub.2                                                                   171-173                                                                               DMSO-d.sub.6 ; 7.75(2H, s)                                                     3.0(6H, s)                                         (19)                                                                               F OCF.sub.2 O                                                                         CSNH.sub.2                                                                          N(CH.sub.3).sub.2                                              (20)                                                                               Br                                                                               OCF.sub.2 O                                                                         CSNH.sub.2                                                                          N(CH.sub.3).sub.2                                              __________________________________________________________________________

                                      TABLE 4                                      __________________________________________________________________________     Benzimidazole derivatives having the formula (I):                                                            1.sup. H-NMR                                                                   (Internal                                        Com-                   Melting                                                                               standard: TMS)                                   pound                  point  Solvent:                                         No. X Z    R    Q      (°C.)                                                                          δ (ppm)                                    __________________________________________________________________________     (21)                                                                               H OCF.sub.2 O                                                                         CN   N(C.sub.2 H.sub.5).sub.2                                                              134-135                                                                               CDCl.sub.3 ; 7.65(1H, s)                                                       7.45(1H, s)                                                                    3.55(4H, q, J=7Hz)                                                             1.20(6H, t, J=7Hz)                               (22)                                                                               H OCF.sub.2 O                                                                         CN   Pyrrolidinyl                                                                          165-170                                                                               CDCl.sub.3 +                                                                   DMSO-d.sub.6 ;                                                                 7.75(2H, s)                                                                    3.40-3.70(4H)                                                                  1.80-2.05(4H)                                    (23)                                                                               H OCF.sub.2 O                                                                         CN   Morpholinyl                                                                           204-210                                                                               CDCl.sub.3 +                                                                   DMSO-d.sub.6 ;                                                          decomposed                                                                            7.80(2H, s)                                                                    3.30-3.90(8H)                                    (24)                                                                               Br                                                                               OCF.sub.2 O                                                                         CN   N(C.sub.2 H.sub.5).sub.2                                                              174    CDCl.sub.3 ; 7.55(1H, s)                                                       3.50(4H, q, J=7Hz)                                                             1.15(6H, t, J=7Hz)                               __________________________________________________________________________

                                      TABLE 5                                      __________________________________________________________________________     Benzimidazole derivatives having the formula (I):                                                           1.sup. H-NMR                                                                   (Internal                                         Com-                  Melting                                                                               standard: TMS)                                    pound                 point  Solvent:                                          No. X Z    R  Q       (°C.)                                                                          δ (ppm)                                     __________________________________________________________________________     (25)                                                                               Br                                                                               OCF.sub.2 O                                                                         CN NCH.sub.3 (C.sub.2 H.sub.5)                                                            168    DMSO-d.sub.6 ;                                                                 7.85(1H, s)                                                                    3.45(2H, q, J=7Hz)                                                             3.00(3H, s)                                                                    1.10(3H, t, J=7Hz)                                (26)                                                                               Br                                                                               OCF.sub.2 O                                                                         CN NCH.sub.3 (CH.sub.2 Ph)                                                                136.1  CDCl.sub.3 ;                                                                   7.55(1H, s)                                                                    7.10-7.40(5H)                                                                  4.50(2H, s)                                                                    2.97(3H, s)                                       (27)                                                                               Br                                                                               OCF.sub.2 O                                                                         CN Pyrrolidinyl                                                                           186.1  DMSO-d.sub.6 ;                                                                 7.90(1H, s)                                                                    3.20-3.70(4H)                                                                  1.70-2.00(4H)                                     (28)                                                                               Br                                                                               OCF.sub.2 O                                                                         CN Morpholinyl                                                                            206    CDCl.sub.3 ;                                                            decomposed                                                                            7.55(1H, s)                                                                    3,70-3.90(4H)                                                                  3.30-3.50(4H)                                     __________________________________________________________________________      Note: Ph represents a phenyl group.                                      

                                      TABLE 6                                      __________________________________________________________________________     Benzimidazole derivatives having the formula (I):                                                             1.sup. H-NMR                                                                   (Internal                                       Com-                      Melting                                                                             standard: TMS)                                  pound                     point                                                                               Solvent:                                        No. X Z      R    Q       (°C.)                                                                        δ (ppm)                                   __________________________________________________________________________     (29)                                                                               H CF.sub.2 CF.sub.2 O                                                                   CN   N(CH.sub.3).sub.2                                                                      132-136                                                                             CDCl.sub.3 ; 8.25(s) 8.05(s)                                                   7.65(s) 7.50(s)                                                                These total                                                                    to 2H, 3.10(6H, s)                              (30)                                                                               H CF.sub.2 CF.sub.2 O                                                                   CN   NCH.sub.3 (C.sub.2 H.sub.5)                                                                 CDCl.sub.3 ; 8.20(s)                                                           8.05(s), 7.63(s)                                                               7.48(s)                                                                        3.53(2H, q, J=8Hz)                                                             3.15(3H, s)                                                                    1.25(3H, t, J=8Hz)                              (31)                                                                               H CF.sub.2 CF.sub.2 O                                                                   CN   NCH.sub.3 (CH.sub.2 Ph)                                                                116.1                                                (32)                                                                               H CF.sub.2 CF.sub.2 O                                                                   CN   Morpholinyl                                                                            151.3                                                (33)                                                                               H CF.sub.2 CF.sub.2 O                                                                   CSNH.sub.2                                                                          N(CH.sub.3).sub.2                                                                           CDCl.sub.3 ; 8.35˜8.50(1H) 8.20(1H,                                      broad)                                                                         7.92(s) 7.88(s) 7.42(s)                                                        7.30(s) These total to 2H,                                                     3.05(6H, s)                                     (34)                                                                               Cl                                                                               OCF.sub.2 CFHO                                                                        CN   N(CH.sub.3).sub.2                                            (35)                                                                               Cl                                                                               OCF.sub.2 CF.sub.2 O                                                                  CN   N(CH.sub.3).sub.2                                            (36)                                                                               Cl                                                                               OCF.sub.2 CFClO                                                                       CN   N(CH.sub.3).sub.2                                            __________________________________________________________________________      Note: Ph represents a phenyl group.                                      

                                      TABLE 7                                      __________________________________________________________________________     Benzimidazole derivatives having the formula (I):                                                           1.sup. H-NMR                                                                   (Internal                                         Com-                         standard: TMS)                                    pound                  Melting                                                                              Solvent:                                          No. X Z      R    Q    point (°C.)                                                                   δ (ppm)                                     __________________________________________________________________________     (37)                                                                               Cl                                                                               OCF.sub.2 CH.sub.2 O                                                                  CN   N(CH.sub.3).sub.2                                            (38)                                                                               H OCF.sub.2 CF.sub.2 O                                                                  CSNH.sub.2                                                                          N(CH.sub.3).sub.2                                            (39)                                                                               Cl                                                                               OCF.sub.2 CF.sub.2 O                                                                  CSNH.sub.2                                                                          N(CH.sub.3).sub.2                                            (40)                                                                               Br                                                                               OCF.sub.2 CF.sub.2 O                                                                  CSNH.sub.2                                                                          N(CH.sub.3).sub.2                                            (41)                                                                               Br                                                                               OCF.sub.2 CFClO                                                                       CN   N(CH.sub.3).sub.2                                            (42)                                                                               Br                                                                               OCF.sub.2 CH.sub.2 O                                                                  CN   N(CH.sub.3).sub.2                                            (43)                                                                               H OCF.sub.2 CFClO                                                                       CSNH.sub.2                                                                          N(CH.sub.3).sub.2                                            (44)                                                                               F OCF.sub.2 CFClO                                                                       CSNH.sub.2                                                                          N(CH.sub.3).sub.2                                            (45)                                                                               Cl                                                                               OCF.sub.2 CFClO                                                                       CSNH.sub.2                                                                          N(CH.sub.3).sub.2                                            (46)                                                                               Br                                                                               OCF.sub.2 CFClO                                                                       CSNH.sub.2                                                                          N(CH.sub.3).sub.2                                            __________________________________________________________________________

                                      TABLE 8                                      __________________________________________________________________________     Benzimidazole derivatives having the formula (I):                                                          1.sup. H-NMR                                                                   (Internal                                          Com-                   Melting                                                                             standard: TMS)                                     pound                  point                                                                               Solvent:                                           No. X Z      R    Q    (°C.)                                                                        δ (ppm)                                      __________________________________________________________________________     (47)                                                                               H OCF.sub.2 CH.sub.2 O                                                                  CSNH.sub.2                                                                          N(CH.sub.3).sub.2                                            (48)                                                                               F OCF.sub.2 CH.sub.2 O                                                                  CSNH.sub.2                                                                          N(CH.sub.3).sub.2                                            (49)                                                                               Cl                                                                               OCF.sub.2 CH.sub.2 O                                                                  CSNH.sub.2                                                                          N(CH.sub.3).sub.2                                            (50)                                                                               Br                                                                               OCF.sub.2 CH.sub.2 O                                                                  CSNH.sub.2                                                                          N(CH.sub.3).sub.2                                            (51)                                                                               Cl                                                                               OCF.sub.2 O                                                                           CN   N(CH.sub.3).sub.2                                            (52)                                                                               Cl                                                                               OCF.sub.2 O                                                                           CSNH.sub.2                                                                          N(CH.sub.3).sub.2                                            (53)                                                                               H CF.sub.2 OCF.sub.2                                                                    CN   N(CH.sub.3).sub.2                                                                   128.5-135                                                                           CDCl.sub.3 ; 8.25(1H, S)                                                       8.15(1H, s)                                                                    3.15(6H, s)                                        (54)                                                                               H CF.sub.2 OCF.sub.2 O                                                                  CN   N(CH.sub.3).sub.2                                            (55)                                                                               H OCF.sub.2 O                                                                           CN   CH.sub.3                                                     (56)                                                                               H CF.sub.2 CF.sub.2 O                                                                   CN   CH.sub.3                                                     (57)                                                                               H OCF.sub.2 CFHO                                                                        CN   CH.sub.3                                                     (58)                                                                               Br                                                                               OCF.sub.2 O                                                                           CN   CH.sub.3                                                     (59)                                                                               F OCF.sub.2 O                                                                           CN   CH.sub.3                                                     __________________________________________________________________________

                                      TABLE 9                                      __________________________________________________________________________     Benzimidazole derivatives having the formula (I):                                                               1.sup. H-NMR                                                                   (Internal                                     Com-                        Melting                                                                             standard: TMS)                                pound                       point                                                                               Solvent:                                      No. X Z      R    Q         (°C.)                                                                        δ (ppm)                                 __________________________________________________________________________     (60)                                                                               F OCF.sub.2 CFHO                                                                        CN   CH.sub.3                                                     (61)                                                                               H OCF.sub.2 O                                                                           CN   CH(CH.sub.3).sub.2                                                                       150.3                                              (62)                                                                               H CF.sub.2 CF.sub.2 O                                                                   CN   CH(CH.sub.3).sub.2                                           (63)                                                                               H OCF.sub.2 CFHO                                                                        CN   CH(CH.sub.3).sub.2                                           (64)                                                                               Br                                                                               OCF.sub.2 O                                                                           CN   CH(CH.sub.3).sub.2                                           (65)                                                                               F OCF.sub.2 O                                                                           CN   CH(CH.sub.3).sub.2                                           (66)                                                                               F OCF.sub.2 CFHO                                                                        CN   CH(CH.sub.3).sub.2                                           (67)                                                                               H OCF.sub.2 O                                                                           CN   NCH.sub.3 (CH.sub.2 C.tbd.CH)                                                            129-131                                            (68)                                                                               F OCF.sub.2 O                                                                           CN   NCH.sub.3 (CH.sub.2 C.tbd.CH)                                (69)                                                                               Br                                                                               OCF.sub.2 O                                                                           CN   NCH.sub.3 (CH.sub.2 C.tbd.CH)                                (70)                                                                               H CF.sub.2 CF.sub.2 O                                                                   CN   NCH.sub.3 (CH.sub.2 C.tbd.CH)                                (71)                                                                               Br                                                                               CF.sub.2 OCF.sub.2                                                                    CN   N(CH.sub.3).sub.2                                            (72)                                                                               Cl                                                                               CF.sub.2 OCF.sub.2                                                                    CN   N(CH.sub.3).sub.2                                            (73)                                                                               H CF.sub.2 OCF.sub.2                                                                    CSNH.sub.2                                                                          N(CH.sub.3).sub.2                                                                             DMSO-d.sub.6 ; 10.7(1H, broad)                                                 10.25(1H, broad)                                                               8.47(1H, s) 8.35(1H, s)                                                        3.08(6H, s)                                   (74)                                                                               H CF.sub.2 OCF.sub.2                                                                    CN   N(C.sub.2 H.sub.5).sub.2                                     (75)                                                                               H CF.sub.2 OCF.sub.2                                                                    CN   NCH.sub.3 (C.sub.2 H.sub.5)                                  (76)                                                                               Br                                                                               CF.sub.2 OCF.sub.2                                                                    CSNH.sub.2                                                                          N(CH.sub.3).sub.2                                            (77)                                                                               Cl                                                                               CF.sub.2 OCF.sub.2                                                                    CSNH.sub.2                                                                          N(CH.sub.3).sub.2                                            (78)                                                                               H CF.sub.2 OCF.sub.2                                                                    CN   CH(CH.sub.3).sub.2                                           __________________________________________________________________________

Next, production examples for the 2-cyanobenzimidazole compound having the formula (II) will be shown.

Intermediate Production Example 1

3.2 Grams of a 2-(trichloromethyl)benzimidazole compound [compound (101)] of the formula (XI) in which X is H and Z is OCF₂ CFHO was dissolved in 30 ml of ethanol. The resulting solution was added by drops to 4 ml of a 25% aqueous ammonia at 5° C. After stirring for 1 hour at 5° to 15° C., the reaction solution was poured into an ice/conc. hydrochloric acid mixture and extrac.ted with ethyl acetate. The organic layer was washed with water and dried over anhydrous sodium sulfate. Removing the solvent from the dried layer by distillation gave 2.83 g of a 2-cyanobenzimidazole compound [compound (i)] of the formula (II) in which X is H and Z is OCF₂ CFHO.

Intermediate Production Example 2

5.3 Grams of 2-(trichloromethyl)benzimidazole compound [compound (104)] of the formula (XI) in which X is H and Z is OCF₂ O was suspended in 100 ml of ethanol. The resulting solution was added by drops to 40 ml of a 25% aqueous ammonia at 5° C. After stirring for 1 hour at 5° C. to room temperature, the reaction solution was poured into an ice/conc. hydrochloric acid mixture and extracted with ethyl acetate. The organic layer was washed with water and dried over anhydrous sodium sulfate. Removing the solvent from the dried layer by distillation gave 4.0 g of a 2-cyanobenzimidazole compound [compound (iv)] of the formula (II) in which X is H and Z is OCF₂ O.

Intermediate Production Example 3

1.0 Gram of a 2-(trichloromethyl)benzimidazole compound [compound (107)] of the formula (XI) in which X is H and Z is CF₂ CF₂ O was dissolved in 20 ml of ethanol. The resulting solution was added by drops to 5 ml of a 25% aqueous ammonia at 5° C. After stirring for 30 minutes at 5° C. the reaction solution was poured into an ice/conc. hydrochloric acid mixture and extracted with ethyl acetate. The organic layer was washed with water and dried over anhydrous sodium sulfate. Removing the solvent from the dried layer by distillation gave 0.6 g of a 2-cyanobenzimidazole compound [compound (vii)] of the formula (II) in which X is H and Z is CF₂ CF₂ O.

Examples of the compounds which can be produced by the above methods will collectively be shown in Table 10.

                  TABLE 10                                                         ______________________________________                                         2-Cyanobenzimidazole compound having the formula (II).                         Compound                 .sup.1 H-NMR (DMSO-d.sub.6, TMS)                      No.     X     Z          δ (ppm)                                         ______________________________________                                         (i)     H     OCF.sub.2 CFHO                                                                            7.70(2H, s) 6.95(1H, dt, J=52,                                                 2Hz)                                                  (ii)    F     OCF.sub.2 CFHO                                                                            7.30(1H, d, J=2Hz) 6.15(1H, dt,                                                J=52, 2Hz)                                            (iii)   Br    OCF.sub.2 CFHO                                                                            7.65(1H, s) 6.80(1H, dt,                                                       J=50, 2Hz)                                            (iv)    H     OCF.sub.2 O                                                                               7.70(2H, s)                                           (v)     F     OCF.sub.2 O                                                                               7.55(1H, s)                                           (vi)    Br    OCF.sub.2 O                                                                               7.75(1H, s)                                           (vii)   H     CF.sub.2 CF.sub.2 O                                                                       7.95(1H, s) 7.20(1H, s)                               (viii)  Cl    OCF.sub.2 O                                                      (ix)    H     OCF.sub.2 CF.sub.2 O                                             (x)     H     OCF.sub.2 CH.sub.2 O                                             (xi)    H     OCF.sub.2 CFClO                                                  (xii)   H     CF.sub.2 OCF.sub.2 O                                                                      8.50(2H, s)                                           (xiii)  H     CF.sub.2 OCF.sub.2 O                                             ______________________________________                                    

Next, production examples for the 2-(trichloromethyl)benzimidazole compound having the formula (XI) will be shown.

Intermediate Production Example 4

2.5 Grams of an o-phenylenediamine compound [compound (201)] of the formula (XII) in which X is H and Z is OCF₂ CFHO was dissolved in 50 ml of acetic acid. 3.8 Grams of methyl trichloroacetoimidate was added thereto at room temperature. The resulting mixture was stirred for 1 hour. The reaction solution was poured into ice water, and precipitated crystals were filtered off. The crystals were dissolved in ethyl acetate. The resulting solution was washed with water and dried over anhydrous sodium sulfate. Removing the solvent from the dried layer by distillation gave 3.2 g of a 2-(trichloromethyl)benzimidazole compound [compound (101)] of the formula (XI) in which X is H and Z is OCF₂ CFHO.

Intermediate Production Example 5

8.6 Grams of an o-phenylenediamine compound [compound (204)] of the formula (XII) in which X is H and Z is OCF₂ O was dissolved in 80 ml of acetic acid. 8.7 Grams of methyl trichloroacetoimidate was added thereto at room temperature. The resulting mixture was stirred for 20 minutes. The reaction solution was poured into ice water, and precipitated crystals were filtered off. The crystals were dissolved in ethyl acetate. The resulting solution was washed with water and dried over anhydrous sodium sulfate. Removing the solvent from the dried layer.by distillation gave 5.35 g of a 2-(trichloromethyl)benzimidazole compound [compound (104)] of the formula (XI) in which X is H and Z is OCF₂ O.

Intermediate Production Example 6

1.0 Gram of an o-phenylenediamine compound [compound (207)] of the formula (XII) in which X is H and Z is CF₂ CF₂ O was dissolved in 20 ml of acetic acid. 1.4 Grams of methyl trichloroacetoimidate was added thereto at room temperature. The resulting mixture was stirred for 12 hours. The reaction solution was poured into ice water, and precipitated crystals were filtered off. The crystals were dissolved in ethyl acetate. The resulting solution was washed with water and dried over anhydrous sodium sulfate. Removing the solvent from the dried layer by distillation gave 1.0 g of a 2-(trichloromethyl)benzimidazole compound [compound (107)] of the formula (XI) in which X is H and Z is CF₂ CF₂ O.

Examples of the 2-(trichloromethyl)benzimidazole compounds which can be produced by the above methods will collectively be shown in Table 11.

                  TABLE 11                                                         ______________________________________                                         2-(Trichloromethyl)benzimidazole                                               compounds having the formula (XI).                                             Compound                 .sup.1 H-NMR (DMSO-d.sub.6, TMS)                      No.     X     Z          δ(ppm)                                          ______________________________________                                         (101)   H     OCH.sub.2 CFHO                                                                            7.65(2H, s) 7.05(1H, dt, J=52,                                                 1Hz)                                                  (102)   F     OCH.sub.2 CFHO                                                                            7.20(1H, d, J=1Hz) 6.30(1H, dt,                                                J=52, 2Hz)                                            (103)   Br    OCH.sub.2 CFHO                                                                            7.40(1H, s) 6.65(1H, dt, J=52,                                                 1Hz)                                                  (104)   H     OCF.sub.2 O                                                                               7.60(2H, s)                                           (105)   F     OCF.sub.2 O                                                                               7.55(1H, s)                                           (106)   Br    OCF.sub.2 O                                                                               7.65(1H, s)                                           (107)   H     CF.sub.2 CF.sub.2 O                                                                       8.35(1H, s) 7.55(1H, s)                               (108)   Cl    OCF.sub.2 O                                                      (109)   H     OCF.sub.2 CF.sub.2 O                                             (110)   H     OCF.sub.2 CH.sub.2 O                                             (111)   H     OCF.sub.2 CFClO                                                  (112)   H     CF.sub.2l OCF.sub.2                                                                       7.90(2H, s)*                                          (113)   H     CF.sub.2 OCF.sub.2 O                                             ______________________________________                                          *CDCl.sub.3 was used as a solvent instead of DMSOd.sub.6.                

Next, production examples for the o-phenylenediamine compound having the formula (XII) will be shown.

Intermediate Production Example 7

2.7 Grams of an o-nitroaniline compound [compound (302)] of the formula (XIV) in which X is Br and Z is OCF₂ CFHO was dissolved in a mixed solvent of 10 ml of ethyl acetate and 10 ml of acetic acid. The resulting solution was added by drops at 40° C. to a suspension of 2.3 g of iron powders in 3 ml of acetic acid and 30 ml of water. After stirring at 50° to 60° C. for 20 minutes, the reaction mixture was filtered through Celite. The filtrate was extracted with ethyl acetate. The organic layer was washed with an aqueous sodium hydrogencarbonate solution and then with water, and dried over anhydrous sodium sulfate. Removing the solvent from the dried layer by distillation gave 2.44 g of an o-phenylenediamine compound [compound (203)] of the formula (XII) in which X is Br and Z is OCF₂ CFHO.

Intermediate Production Example 8

2.97 Grams of an o-nitroaniline compound [compound (305)] of the formula (XIV) in which X is Br and Z is OCF₂ O was dissolved in a mixed solvent of 10 ml of ethyl acetate and 10 ml of acetic acid. The resulting solution was added by drops at 40° C. to a suspension of 2.4 g of iron powders in 2 ml of acetic acid and 20 ml of water. After stirring at 40° C. to 55° C. for 30 minutes, the reaction mixture was filtered through Celite. The filtrate was extracted with ethyl acetate. The organic layer was washed with an aqueous sodium hydrogencarbonate solution and then with water, and dried over anhydrous sodium sulfate. Removing the solvent from the dried layer by distillation gave 2.52 g of an o-phenylenediamine compound [compound (206)] of the formula (XII) in which X is Br and Z is OCF₂ O.

Intermediate Production Example 9

1.1 Grams of an o-nitroaniline compound having the formula (XXIV), ##STR22## was dissolved in a mixed solvent of 15 ml of ethyl acetate and 15 ml of acetic acid. The resulting solution was added by drops at 50° C. to a suspension of 1 g of iron powders in 2 ml of acetic acid and 30 ml of water. After stirring at 50° to 60° C. for 10 minutes, the reaction mixture was filtered through Celite. The filtrate was extracted with ethyl acetate. The organic layer was washed with an aqueous sodium hydrogencarbonate solution and then with water, and dried over anhydrous sodium sulfate. Removing the solvent from the dried layer by distillation gave 1.0 g of an o-phenylenediamine compound [compound (207)] of the formula (XII) in which X is H and Z is CF₂ CF₂ O.

The o-phenylenediamine compounds which can be produced by the above methods will be shown in Table 12.

                  TABLE 12                                                         ______________________________________                                         o-Phenylenediamine compounds having the formula (XII).                         Com-                                                                           pound                     .sup.1 H-NMR (CDCl.sub.3, TMS)                       No.    X      Z           δ(ppm)                                         ______________________________________                                         (201)  H      OCH.sub.2 CFHO                                                                             6.40(2H, s)                                                                    5.70(1H, dt, J=57, 1Hz)                                                        3.30(4H, broad)                                      (202)  F      OCH.sub.2 CFHO                                                                             6.40(1H, d, J=2Hz)                                                             5.9(1H, dt, J=52, 1Hz)                                                         3.55(4H, broad)                                      (203)  Br     OCH.sub.2 CFHO                                                                             6.45(1H, s)                                                                    5.85(1H, dt, J=53, 2Hz)                              (204)  H      OCF.sub.2 O 6.50(2H, s) 3.30(4H, broad)                          (205)  F      OCF.sub.2 O 6.28(1H, d, J=1Hz)                                                             3.35(4H, broad)                                      (206)  Br     OCF.sub.2 O 6.45(1H, s) 3.50(4H, broad)                          (207)  H      CF.sub.2 CF.sub.2 O                                                                        6.85(1H, s) 6.30(1H, s)                                                        3.20(4H, broad)                                      (208)  Cl     OCF.sub.2 O                                                      (209)  H      CF.sub.2 OCF.sub.2                                                                         6.90(2H, s) 3.85(4H, broad)                          ______________________________________                                    

Next, production examples for the o-nitroaniline compound having the formula (XIV) will be shown.

Intermediate Production Example 10

A mixture of 5.07 g of an o-nitroanilide compound [compound (401)] of the formula (XVI) in which X is H, Z is OCF₂ CFHO and R² is CH₃, 10 ml of conc. hydrochloric acid and 100 ml of methanol was heated under reflux for 1 hour. The reaction solution was concentrated, poured into ice water and alkalified with potassium carbonate. After extraction with ethyl acetate, the organic layer was washed with water and dried over anhydrous sodium sulfate. Removing the solvent from the dried layer by distillation gave 4.23 g of a compound [compound (301)] of the formula (XIV) in which X is H and Z is OCF₂ CFHO.

Intermediate Production Example 11

2.67 Grams of the compound (301) was dissolved in 30 ml of acetic acid. To the resulting solution was added by drops 0.3 ml of bromine at room temperature. After addition, stirring was continued for 3 hours at room temperature. The reaction solution was poured into ice water, and precipitated crystals were filtered off. The crystals were dissolved in ethyl acetate. The resulting solution was washed with water and dried over anhydrous sodium sulfate. Removing the solvent from the dried layer by distillation gave 2.7 g of an o-nitroaniline compound [compound (302)] of the formula (XIV) in which X is Br and Z is OCF₂ CFHO.

Intermediate Production Example 12

A mixture of 7.69 g of an o-nitroanilide compound [compound (402)] of the formula (XVI) in which X is H, Z is OCF₂ O and R² is CH₃, 10 ml of conc. hydrochloric acid and 90 ml of methanol was heated under reflux for 1.5 hours. The reaction solution was concentrated, poured into ice water and alkalifled with potassium carbonate. After extraction with ethyl acetate, the organic layer was washed with water and dried over anhydrous sodium sulfate. Removing the solvent from the dried layer by distillation gave 4.65 g of a compound [compound (303)] of the formula (XIV) in which X is H and Z is OCF₂ O.

Intermediate Production Example 13

2.18 Grams of the compound (303) was dissolved in 35 ml of acetic acid. To the resulting solution was added by drops 2 ml of bromine at room temperature. After addition, stirring was continued for 2.5 hours at room temperature to 40° C. The reaction solution was poured into ice water, and precipitated crystals were filtered off. The crystals were dissolved in ethyl acetate. The resulting solution was washed with water and dried over anhydrous sodium sulfate. Removing the solvent from the dried layer by distillation gave 2.50 g of an o-nitroaniline compound [compound (305)] of the formula (XIV) in which X is Br and Z is OCF₂ O.

Intermediate Production Example 14

A mixture of 1.32 g of an o-nitroacetoanilide compound having the formula (XXV), ##STR23## 5 ml of conc. hydrochloric acid and 50 ml of methanol was heated under reflux for 80 minutes. The reaction solution was concentrated, poured into ice water and alkalifled with potassium carbonate. After extraction with ethyl acetate, the organic layer was washed with water and dried over anhydrous sodium sulfate. Removing the solvent from the dried layer by distillation gave 1.1 g of an o-nitroaniline compound [compound (306)] having the formula (XXIV).

Intermediate Production Example 15

200 Grams of an o-dinitro compound having the formula (XV) in which X is H and Z is OCF₂ O was dissolved in 900 ml of N,N-dimethylformamide. The resulting solution was allowed to react at 70° C. for 3 and a half hours while blowing ammonia thereinto. Thereafter, the reaction solution was cooled to room temperature. The cooled solution was filtered through Celite. The filtrate was extracted with diethyl ether. The organic layer was washed with water and dried over anhydrous sodium sulfate. Removing the solvent from the dried layer by distillation gave a residue. The, residue was subjected to silica gel column chromatography using chloroform as an eluent to obtain 112.4 g of an o-nitroaniline compound [Compound (303)] having the formula (XIV) in which X is H and Z is OCF₂ O.

Intermediate Production Example 16

1.60 Grams of an o-chloronitro compound having the formula (XXVI), ##STR24## was dissolved in 30 ml of N,N-dimethylformamide. The resulting solution was allowed to react at 90° C. for 1 hour while blowing ammonia thereinto. Thereafter, the reaction solution was poured into ice water and extracted with ethyl acetate. The organic layer was washed with water. The washed layer was dried over anhydrous sodium sulfate. Removing the solvent from the dried layer by distillation gave a residue. The residue was subjected to silica gel column chromatography using dichloromethane as an eluent to obtain 0.8 g of an o-nitroaniline compound .[Compound (308)] having the formula (XIV) in which X is H and Z is CF₂ OCF₂.

The compounds which can be produced by the above methods will be collectively shown in Table 13.

                  TABLE 13                                                         ______________________________________                                         o-Nitroaniline compounds having the formula (XIV).                             Com-                                                                           pound                     .sup.1 H-NMR (CDCl.sub.3, TMS)                       No.    X      Z           δ(ppm)                                         ______________________________________                                         (301)  H      OCH.sub.2 CFHO                                                                             7.90(1H, s) 7.00(2H, broad)                                                    6.80(1H, s)                                                                    6.10(1H, dt, J=52, 1Hz)                              (302)  Br     OCH.sub.2 CFHO                                                                             8.05(1H, s) 6.65(.2H, broad)                                                   5.95(1H, dt, 3=52, 2Hz)                              (303)  H      OCF.sub.2 O 7.85(1H, s) 6.50(1H, s)                                                        6.35(2H, broad)                                      (304)  F      OCF.sub.2 O 7.65(1H, d, J=2Hz)                                                             6.30(2H, broad)                                      (305)  Br     OCF.sub.2 O 7.90(1H, s) 6.85(2H, broad)                           (306)*                                                                               H      CF.sub.2 CF.sub.2 O                                                                        7.80(1H, s) 7.10(1H, s)                                                        6.10(2H, broad)                                      (307)  Cl     OCF.sub.2 O                                                      (308)  H      CF.sub.2 OCF.sub.2                                                                         8.40(1H, s) 7.05(1H, s)                                                        6.50(2H, broad)                                      ______________________________________                                          Note: *Compound (306) is a compound having the formula (XXIV).           

Next, production examples for the o-nitroacetoanilide compound having the formula (XVI) will be shown.

Reference Example 1

4.31 Grams of an anilide compound (compound (501)] of the formula (XVIII) in which X is H, Z is OCF₂ CFHO and R² is CH₃ was added to 50 ml of conc. sulfuric acid. To the resulting mixture was added by drops a mixture of 3.5 ml of fuming nitric acid and 7 ml of conc. sulfuric acid at -15° C. After addition, stirring was continued for 2 hours at -15° to -10° C. The reaction solution was poured into ice water, and precipitated crystals were filtered off. The crystals were dissolved in ethyl acetate. The resulting solution was washed with water and dried over anhydrous sodium sulfate. A residue was obtained by removing the solvent from the dried layer by distillation. Column chromatographying the residue on silica gel with chloroform as an eluent gave 5.07 g of an o-nitroanilide compound [compound (401)] of the formula (XVI) in which X is H, Z is OCF₂ CFHO and R² is CH.sub. 3.

Reference Example 2

8.9 Grams of an anilide compound [compound (502)] of the formula (XVIII) in which X is H, Z is OCF₂ O and R² is CH₃ was added to 80 ml of conc. sulfuric acid. To the resulting mixture was added by drops a mixture of 7.5 ml of fuming nitric acid and 15 ml of conc. sulfuric acid at 0° C. After addition, stirring was continued for 0.5 hour at -10° to 0° C. The reaction solution was poured into ice water, and precipitated crystals were filtered off. The crystals were dissolved in ethyl acetate. The resulting solution was washed with water and dried over anhydrous sodium sulfate. A residue was obtained by removing the solvent from the dried layer by distillation. Column chromatographying the residue on silica gel with chloroform as an eluent gave 7.69 g of an o-nitroanilide compound [compound (402)] of the formula (XVI) in which X is H, Z is OCF₂ O and R² is CH₃.

Reference Example 3

2.69 Grams of an anilide compound having the formula (XXVII), ##STR25## was added to 50 ml of conc. sulfuric acid. To the resulting mixture was added by drops a mixture of 2.5 ml of fuming nitric acid and 5 ml of conc. sulfuric acid at -10° C. After addition, stirring was continued for 1 hour at -10° to 0° C. The reaction solution was poured into ice water, and precipitated crystals were filtered off. The crystals were dissolved in ethyl acetate. The resulting solution was washed with water and dried over anhydrous sodium sulfate. A residue was obtained by removing the solvent from the dried layer by distillation. Column chromatographying the residue on silica gel with chloroform as an eluent gave 1.32 g of an o-nitroacetoanilide compound [compound (404)] of the formula (XXV).

The compound(404) can also be produced by the method shown in Reference Example 4.

Reference Example 4

7.80 Grams of a compound of the formula (XX) in which Y is Cl and R² is CH₃ was dissolved in 70 ml of N,N-dimethylformamide. 8.0 Grams of copper powders and 0.5 g of 2,2'-bipyridyl were added thereto. Thereafter, stirring was continued at 140° C. for 2 hours. After completion of the reaction, the reaction solution was filtered through Celite. The filtrate was extracted with diethyl ether. The organic layer was washed with water and dried over anhydrous sodium sulfate. A residue was obtained by removing the solvent from the dried layer by distillation. Column chromatographying the residue on silica gel with chloroform as an eluent and recrystallizing it from hexane/ethyl acetate gave 3.06 g of an o-nitroanilide compound compound (404)] having the formula (XXV).

The compounds produced by the above methods will be collectively shown in Table 14.

                  TABLE 14                                                         ______________________________________                                         o-Nitroanilide compounds having the formula (XVI).                             Com-                                                                           pound                       .sup.1 H-NMR (CDCl.sub.3, TMS)                     No.   X     Z          R.sup.2                                                                             δ(ppm)                                       ______________________________________                                         (401) H     OCF.sub.2 CFHO                                                                            CH.sub.3                                                                            10.35(1H, broad) 8.70(1H, s)                                                   8.00(1H, s) 6.00(1H, dt, J=50,                                                 1Hz) 2.30(3H, s)                                   (402) H     OCF.sub.2 O                                                                               CH.sub.3                                                                            10.55(1H, broad) 8.70(1H, s)                                                   7.97(1H, s) 2.30(3H, s)                            (403) F     OCF.sub.2 O                                                                               CH.sub.3                                                                            9.60(1H, broad) 7.65(1H, d,                                                    J=2Hz) 2.20(3H, s)                                  (404)*                                                                              H     CF.sub.2 CF.sub.2 O                                                                       CH.sub.3                                                                            10.05(1H, broad) 8.75(1H, s)                                                   7.75(1H, s) 3H, s)                                 ______________________________________                                          Note: *Compound (404) is a compound having the formula (XXV).            

Next, production examples for the anilide compound having the formula (XVIII) will be shown.

Reference Example 5

4.8 Grams of an aniline compound of the formula (XXI) in which X is H and Z is OCF₂ CFHO was dissolved in 50 ml of acetic acid and 2.4 ml of acetic anhydride. The resulting solution was stirred at 70° C. for 10 minutes. The reaction solution was poured into ice water and extracted with ethyl acetate. The organic layer was washed with water and dried over anhydrous sodium sulfate. A residue was obtained by removing the solvent from the dried layer by distillation. Column chromatographying the residue on silica gel with chloroform and ethyl acetate as an eluent gave 4.31 g of an anilide compound [compound (501)] of the formula (XVIII) in which X is H, Z is OCF₂ CFHO and R² is CH₃.

Reference Example 6

8.4 Grams of an aniline compound of the formula (XXI) in which X is H and Z is OCF₂ O was dissolved in 100 ml of acetic acid and 5 ml of acetic anhydride. The resulting solution was stirred at 60° C. for 5 minutes. The reaction solution was poured into ice water and extracted with ethyl acetate. The organic layer was washed with water and dried over anhydrous sodium sulfate. A residue was obtained by removing the solvent from the dried layer by distillation. Column chromatographying the residue on silica gel with chloroform and ethyl acetate as an eluent gave 8.93 g of an anilide compound [compound (502)] of the formula (XVIII) in which X is H, Z is OCF₂ O and R² is CH₃.

The anilide compounds produced by the above methods will collectively be shown in Table 15.

                  TABLE 15                                                         ______________________________________                                         Anilide compounds having the formula (XVIII).                                  Com-                                                                           pound                       .sup.1 H-NMR (Internal standard:                   No.   X     Z          R.sup.2                                                                             TMS) Solvent: δ(ppm)                         ______________________________________                                         (501) H     OCF.sub.2 CFHO                                                                            CH.sub.3                                                                            CDCl.sub.3 + DMSO-d.sub.6 : 9.90(1H,                                           broad) 7.60(1H, d, J=2Hz)                                                      7.25(1H, dt, J=8, 2Hz)                                                         7.00(1H, d, J=8Hz) 6.30(1H,                                                    dt, J=52, 1Hz) 2.10(3H, s)                         (502) H     OCF.sub.2 O                                                                               CH.sub.3                                                                            CDCl.sub.3 ; 9.55(1H, broad)                                                   7.65(1H, d, J=1Hz)                                                             7.15(1H, dd, J=8, 1Hz)                                                         6.95(1H, d, J=8Hz) 2.15(3H, s)                     (503) F     OCF.sub.2 O                                                                               CH.sub.3                                                                            CDCl.sub.3 ; 7.80(1H, dd, J=8,                                                 8Hz) 7.60(1H, broad) 6.80(1H,                                                  dd, J=8, 1Hz) 2.20(3H, s)                          ______________________________________                                    

Formulation examples will be shown. In the examples, parts are by weight.

Formulation Example 1

Thoroughly pulverizing and mixing 50 parts of each of the present compounds (1) to (78), 3 parts of calcium lignosulfonate, 2 parts of sodium lauryl sulfate and 45 parts of synthetic hydrated silicon dioxide give a wettable powder of each of the present compounds.

Formulation Example 2

25 Parts of each of the present compounds (1) to (78), 3 parts of polyoxyethylene sorbitan monooleate, 3 parts of CMC and 69 parts of water are mixed. Wet-pulverizing the resulting mixture until the particle size of the active ingredient is reduced to 5 microns or less gives a suspension formulation of each of the present compounds.

Formulation Example 3

Thoroughly pulverizing and mixing 2 parts of each of the present compounds (1) to (78), 88 parts of kaolin clay and 10 parts of talc give a dust of each of the present compounds.

Formulation Example 4

Thoroughly mixing 20 parts of each of the present compounds (1) to 78), 14 parts of polyoxyethylene styrylphenyl ether, 6 parts of calcium dodecylbenzenesulfonate and 60 parts of xylene gives an emulsifiable concentrate of each of the present compounds.

Formulation Example 5

2 Parts of each of the present compounds (1) to (78), 1 part of synthetic hydrated silicon dioxide, 2 parts of calcium lignosulfonate, 30 parts of bentonire and 65 parts of kaolin clay are well pulverized and mixed. The resulting mixture is well kneaded with water, granulated and dried to obtain a granule of each of the present compounds.

Next, the usefulness of the present compound as an agricultural and horticultural fungicide will be shown by test examples. As a control, mancozeb (wettable powder) commonly used as a Phycomycetes-controlling agent was used. The controlling activity in Test Examples 1 to 4 was evaluated in six stages, 5, 4, 3, 2, 1, 0, of the controlling index by macroscopically observing the condition of disease of the test plants, i.e. the degrees of colony and infected area on the leaves, stems, etc., at the time of examination.

5 Infected area is not observed at all.

4 Size of infected area is less than 10% of that in the untreated plot.

3 Size of infected area is less than 30% of that in the untreated plot.

2 Size of infected area is less than 50% of that in the untreated plot.

1 Size of infected area is less than 75% of that in the untreated plot.

0 Size of infected area is 75% or more of that in the untreated plot.

Test Example 1 Controlling test on late blight of tomato (Phytophthora infestans) (preventive effect)

Sandy loam was filled in plastic pots, and tomato (var., Ponterosa) was sowed and cultivated for 20 days in a greenhouse to obtain tomato seedlings in the 2nd to 3rd true leaf stage. Thereafter, the wettable powder of the test compound prepared according to Formulation Example 1 was diluted with water to a prescribed concentration and foliar-applied onto the seedlings so that the spray liguor thoroughly adhered to the leaf surface. After the spraying, the seedlings were inoculated by spraying the spore suspension of Phytophthora infestans. After the inoculation, the seedlings were kept in conditions of 20° C. and high humidity for 1 day and further cultivated for 7 days under lighting. The controlling activity was then examined. The results are shown in Table 16.

                  TABLE 16                                                         ______________________________________                                                  Controlling activity                                                  Compound   12.5         3.1   0.8 ppm                                          ______________________________________                                          (1)       4            2     1                                                 (2)       5            4     3                                                 (3)       5            4     3                                                (15)       5            4     1                                                (16)       5            5     4                                                (17)       5            4     4                                                (29)       5            4     1                                                (53)       5            5     4                                                Mancozeb   3            0     0                                                ______________________________________                                    

Test Example 2 Controlling test on late blight of tomato (Phytophthora infestans) (curative effect)

Sandy loam was filled in plastic pots, and tomato (var., Ponterosa) was sowed and cultivated for 20 days in a greenhouse to obtain tomato seedlings in the 2nd to 3rd true leaf stage. The seedlings were inoculated by spraying the spore suspension of phytophthora infestans. After the inoculation, the seedlings were kept in conditions of 20° C. and high humidity for 1 day. Thereafter, the wettable powder of the test compound prepared according to Formulation Example 1 was diluted with water to a prescribed concentration and foliar-applied onto the seedlings so that the spray liquor thoroughly adhered to the leaf surface. After the spraying, the seedlings were cultivated for 7 days under lighting. The controlling activity was then examined. The results are shown in Table 17.

                  TABLE 17                                                         ______________________________________                                                  Controlling activity                                                  Compound   200          50    12.5 ppm                                         ______________________________________                                          (1)       3            0     0                                                 (2)       4            4     1                                                (15)       3            2     0                                                (16)       5            4     3                                                (17)       5            4     3                                                (29)       5            5     3                                                (53)       5            5     3                                                Mancozeb   0            0     0                                                ______________________________________                                    

Test Example 3 Controlling test on downy mildew of grape (Plasmopara viticola) (preventive effect)

Sandy loam was filled in plastic pots, and grape was sowed and cultivated for 50 days in a greenhouse to obtain grape seedlings in the 3rd to 4th true leaf stage. Thereafter, the wettable powder of the test compound prepared according to Formulation Example 1 was diluted with water to a prescribed concentration and foliar-applied onto the seedlings so that the spray liquor thoroughly adhered tothe leaf surface. After the spraying, the seedlings were inoculated by spraying the spore suspension of Plasmopara viticola. After the inoculation, the seedlings were kept in conditions of 20° C. and high humidity for 1 day and further cultivated for 7 days under lighting. The controlling activity was then examined. The results are shown in Table 18.

                  TABLE 18                                                         ______________________________________                                                  Controlling activity                                                  Compound   12.5         3.1   0.8 ppm                                          ______________________________________                                          (1)       5            1     0                                                 (2)       5            3     1                                                 (3)       5            4     3                                                (15)       4            1     0                                                (16)       5            4     2                                                (17)       5            5     2                                                (29)       5            5     3                                                (53)       5            5     4                                                Mancozeb   2            0     0                                                ______________________________________                                    

Test Example 4 Controlling test on downy mildew of grape (Plasmopara viticola) (curative effect)

Sandy loam was filled in plastic pots, and grape was sowed and cultivated for 50 days in a greenhouse to obtain grape seedlings in the 3rd to 4th true leaf stage. The seedlings were inoculated by spraying the spore suspension of Plasmopara viticola. After the inoculation, the seedlings were kept in conditions of 20° C. and high humidity for 1 day. Thereafter, the wettable powder of the test compound prepared according to Formulation Example 1 was diluted with water to a prescribed concentration and foliar-applied onto the seedlings so that the spray liquor thoroughly adhered to the leaf surface. After the spraying, the seedlings were cultivated for 7 days under lighting. The controlling activity was then examined. The results are shown in Table 19.

                  TABLE 19                                                         ______________________________________                                                  Controlling activity                                                  Compound   200          50    12.5 ppm                                         ______________________________________                                          (1)       3            1     0                                                 (2)       5            2     1                                                (15)       4            4     0                                                (16)       5            5     4                                                (17)       5            5     4                                                (29)       5            5     3                                                (53)       5            5     5                                                Mancozeb   0            0     0                                                ______________________________________                                    

Referential Test Example 1

Controlling test on late blight of tomato (Phytophthora infestans) (preventive effect; effect of mixing with various fungicides)

Sandy loam was filled in plastic pots. Tomato (var., Ponterosa) was sowed therein and cultivated for 30 days in a greenhouse to obtain tomato seedlings in the 4th to 5th true leaf stage.

Wettable powders containing one of the present compounds formulated according to Formulation Example 1, various kinds of commercially available fungicide and one of the present compounds and one of the commercially available fungicides were diluted with water to a prescribed concentration. Thereafter, they were foliar-applied onto the seedlings so that the spray liquor thoroughly adhered to the leaf surface. After the spraying, the seedlings were placed for 6 days in a greenhouse. Then, they were inoculated by spraying the spore suspension of Phytophthora infestans. After the inoculation, the seedlings were kept in conditions of 20° C. and high humidity for 1 day and further cultivated for 6 days under lighting. For the lowest four true leaves, the following disease indices were determined by their infected areas. Then, the disease severity (%) was defined by the equation 1 below. Further, from the disease severities of the treated and untreated seedlings, the control of disease (%) was defined by the equation 2 below. Table 20 shows the results.

Disease index 5 Outbreak of disease in 90% or more of the true leaves.

Disease index 4 Outbreak of disease in less than 90% of the true leaves.

Disease index 3 Outbreak of disease in less than 60% of the true leaves.

Disease index 2 Outbreak of disease in less than 30% of the true leaves.

Disease index 1 Outbreak of disease in less than 10% of the true leaves.

Disease index 0.5 Outbreak of disease in less than 5% of the true leaves.

Disease index 0 No outbreak of disease ##EQU1##

                  TABLE 20                                                         ______________________________________                                         Test compound                                                                                 Concentration                                                                  of active    Control of                                         Compound       ingredient (ppm)                                                                            disease (%)                                        ______________________________________                                         (15)            25          76.2                                               (17)            25          92.5                                               "               5           68.1                                               Chlorothalonil (A)                                                                            300          85.6                                               Fluazinam (B)  150          65.0                                               Dichlofluanide (C)                                                                            200          84.4                                               Phosethyl-     400          0.0                                                aluminum (D)                                                                   Captan (E)     500          76.2                                               Mancozeb (F)   600          92.5                                               Basic cupric   600          46.2                                               chloride (G)                                                                   (A) + (17)     300 + 25     97.5                                               (B) + (15)     150 + 25     85.4                                               (C) + (15)     200 + 25     91.2                                               (D) + (17)     400 + 5      81.9                                               (E) + (15)     500 + 25     95.0                                               (F) + (17)     600 + 25     100.0                                              (G) + (15)     600 + 25     80.7                                               ______________________________________                                    

Referential Test Example 2

Controlling test on downy mildew of cucumber (Pseudoperonospora cubensis) (curative and preventive effect); effect of mixing with various fungicides)

Sandy loam was filled in plastic pots. Cucumber (var., Sagamihanjiro) was sowed therein and cultivated for 30 days in a greenhouse to obtain cucumber seedlings in the 4th true leaf stage. Thereafter, the seedlings were inoculated by spraying the spore suspension of Pseudoperonospora cubansis. After the inoculation, the seedlings were kept in conditions of 20° C. and high humidity for 1 day. Wettable powders containing one of the present compounds formulated according to Formulation Example 1, various kinds of commercially available fungicide and mixtures of one of the present compounds and one of the commercially available fungicides were diluted with water to a prescribed concentration. Thereafter, they were foliar-applied onto the seedlings so that the spray liquor thoroughly adhered to the leaf surface. After the spraying, the seedlings were placed for 6 days in a greenhouse. Then, they were inoculated again by spraying the spore suspension of Pseudoperonospora cubensis. After the re-inoculation, the seedlings were kept in conditions of 20° C. and high humidity for 1 day and further cultivated for 7 days under lighting. For the lowest second, third and fourth true leaves, the disease indices were determined by their infected areas. Then, the disease severity (%) was defined by the equation 3 below. Further, from the disease severities of the treated and untreated seedlings, the control of disease (%) was defined by the equation 4 below. Table 21 shows the results.

Disease index 10 Outbreak of disease in 90% or more of the true leaves.

Disease index 9 Outbreak of disease in less than 90% of the true leaves.

Disease index 8 Outbreak of disease in less than 80% of the true leaves.

Disease index 7 Outbreak of disease in less than 70% of the true leaves.

Disease index 6 Outbreak of disease in less than 60% of the true leaves.

Disease index 5 Outbreak of disease in less than 50% of the true leaves.

Disease index 4 Outbreak of disease in less than 40% of the true leaves.

Disease index 3 Outbreak of disease in less than 30% of the true leaves.

Disease index 2 outbreak of disease in less than 20% of the true leaves.

Disease index 1 Outbreak of disease in less than 10% of the true leaves.

Disease index 0.5 Outbreak of disease in less than 5% of the true leaves.

Disease index 0 No outbreak of diseases.

                  TABLE 21                                                         ______________________________________                                         Test compound                                                                                  Concentration                                                                  of active    Control of                                        Compound        ingredient (ppm)                                                                            disease (%)                                       ______________________________________                                         (15)            200          53.5                                              "               100          21.1                                              (17)            200          99.2                                              "               100          96.5                                              N-[cyano(2'-furyl)-                                                                            200          86.0                                              methyl]-2,4-dimethyl-                                                          thiazole-5-carboxy-                                                                            100          75.5                                              amide (H)                                                                      Cymoxanil (I)   200          76.3                                              "               100          42.1                                              Metalaxyl (J)   200          92.1                                              "               100          91.3                                              (H) + (15)      100 + 100    100.0                                             "               50 + 50      100.0                                             (H) + (17)      100 + 100    100.0                                             "               50 + 50      100.0                                             (I) + (15)      100 + 100    98.2                                              (I) + (17)      100 + 100    100.0                                             "               50 + 50      100.0                                             (J) + (15)      100 + 100    98.2                                              (J) + (17)      100 + 100    100.0                                             "               50 + 50      100.0                                             ______________________________________                                          ##EQU2##

The present compound has excellent controlling effect on various plant diseases, particularly plant diseases caused by Phycomycetes such as downy mildew, late blight and the like, and further gives no such phytotoxicity as would become a problem to crops. Consequently, the present compound can be applied to various uses as an active ingredient for agricultural and horticultural fungicides. 

What is claimed is:
 1. An o-phenylenediamine compound having the formula, ##STR26## wherein X¹ is halogen.
 2. An o-nitroaniline compound having the formula, ##STR27## wherein X¹ is as defined in claim
 1. 3. A. compound of the formula ##STR28##
 4. A compound of the formula ##STR29## 